Method of (111) group II-VI epitaxial layer grown on (111) silicon substrate

ABSTRACT

A group II-VI epitaxial layer grown on a (111) silicon substrate has a lattice mismatch which is minimized, as between the group II-VI epitaxial layer and the silicon substrate. The grown group II-VI epitaxial layer also has a (111) plane at the interface with the substrate, and a 30° in-plane rotation slip is formed at the interface between the (111) silicon substrate and the group II-VI epitaxial layer. The above structure is produced by a metal organic chemical vapor deposition method (MOCVD), in which a mol ratio of a group VI gas source supply to a group II gas source supply is kept greater than 15 during the growth. The (111) silicon substrate is preferably mis-oriented toward the &lt;110&gt; direction of the silicon substrate. When a HgCdTe layer is grown on the epitaxial layer, the product thus formed has utility as a monolithic infrared detector in which a plurality of detector elements are formed in the HgCdTe layer and a signal processing circuit is formed in the silicon substrate.

This application is a division of application Ser. No. 07/987,683, filedDec. 9, 1992, now U.S. Pat. No. 5,302,232.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a group II-VI epitaxial layer grown ona silicon substrate. More particularly, the present invention relates toa (111) CdTe epitaxial layer grown on a (111) silicon substrate. HgCdTeis known as a sensitive material for infrared detection, and HgCdTehetero-epitaxial growth on a silicon substrate is a key technology fordevelopment of monolithtic infrared detectors. For this purpose, a CdTebuffer layer is first grown on a silicon substrate, and thereafter theHgCdTe layer is grown on the CdTe epitaxial layer.

2. Description of the Related Art

A conventional infrared imager of a hybrid type has a structure suchthat a plurality of infrared detector elements of HgCdTe are formed on aCdTe substrate and a signal processing arrangement, for example, a CCDis formed on a silicon substrate, and two substrates are integratedtogether using a plurality of bumps forming the infrared imager.

In response to requirements for an increased number of detector elementsin order to improve resolution in image detection, an infrared imager ofa monolithic type has been proposed. The monolithic infrared imagerutilizes a CdTe buffer layer grown on a silicon substrate, and a HgCdTelayer is grown on the CdTe buffer layer. A signal processing arrangementis formed in the silicon substrate and a plurality of detector elementsare formed in the HgCdTe layer. The monolithic infrared imager can copewith the increased number of detector elements, and enables simplermanufacturing processes and increases mechanical reliability.

The basic problem in production of the monolithtic infrared imager is toachieve hetero-epitaxial growth of CdTe on a silicon substrate. It iswell known that the crystal structure of silicon is of a diamond typeand the crystal structure of CdTe is of a zinc-blende type. These twotypes have sufficient resemblance in lattice structures such that, ifboth two kinds of atoms of the zinc-blende type are replaced withsilicon atoms, the crystal has the same structure as the diamond type ofsilicon.

In growing a CdTe epitaxial layer on a silicon substrate, the followingmethods are known, in which the grown CdTe layer has the same crystalorientation as that of silicon substrate. When a silicon substratehaving a (100) plane is used, a CdTe epitaxial layer with a (100) planeis grown thereon. When a (111) silicon substrate is used, a (111) CdTeepitaxial layer is grown thereon. In both cases, the grown CdTe layerhas the same in-plane direction as the crystal direction of theunderlying silicon substrate. One aspect of these technologies isdisclosed in "Growth of CdTe films on silicon by molecular beam epitaxy"by H. H. Stadelmaier, J.Apple.Phys. 54(7), July 1983, pp. 4238-4240.

The above methods include a basic problem that a lattice mismatchbetween silicon and CdTe can not be avoided. In the above case, thelattice mismatch runs to about 19%. It is known that GaAs has the samezinc-blende structure as CdTe and can be used as a substrate or a bufferlayer on a silicon substrate. However, the lattice mismatch between GaAsand CdTe is reduced only to 14.6%.

The large lattice mismatch as described above causes crystalline defectssuch as misfit and dislocation. Other methods of growing a CdTeepitaxial layer with a different crystal orientation from that of asubstrate have been tried; however; there still remains a latticemismatch problem.

SUMMARY OF THE INVENTION

It is a general object of the present invention to provide a group II-VIepitaxial layer on a silicon substrate.

It is another object of the invention to provide a CdTe epitaxial layeron a silicon substrate, wherein a lattice mismatch between CdTe andsilicon is minimized.

It is further object of the invention to provide a method of growing aCdTe epitaxial layer which is lattice-matched with the underlyingsilicon substrate.

The above objects can be achieved by the invention, wherein a (111)silicon substrate is used and a (111) CdTe epitaxial layer is grownthereon, the grown CdTe layer having a 30° in-plane rotation slip withrespect to the underlying silicon crystal orientation.

The growth is performed by a metal organic chemical vapor depositionmethod (MOCVD), in which dimethylcadmium (DMCd) and diethyltelluride(DETe) are used as the cadmium and tellurium sources. The (111) siliconsubstrate is annealed in a hydrogen atmosphere at 1000° C., andthereafter the substrate temperature is reduced to 400° C. and DMCd andDETe source gases are introduced, wherein a mol ratio of the sourcegases during the growth, namely, DETe/DMCd, is selected to be greaterthan 15.

According to the present invention, the surface of (111) siliconsubstrate is preferably mis-oriented by 1° to 10° toward the <110>direction.

Other objects and advantages of the present invention will be apparentfrom the following description, the appended claims and the accompanyingdrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic top view of a lattice structure at theinterface between a CdTe epitaxial layer and a silicon substrate, inwhich a 30° in-plane rotation slip is formed in the interface;

FIG. 2 is a perspective view of a composite crystal structure of thesilicon substrate and the epitaxial layer illustrating schematically theabove rotation slip;

FIGS. 3(a) and 3(b) show are schematic cross sections of the siliconsubstrate illustrating mis-orientation of the (111) silicon substrate,wherein FIG. 3(a) shows a case without the mis-orientation, and FIG.3(b) shows a <111> direction of the silicon substrate which ismis-oriented toward <110> direction thereof;

FIG. 4 shows a test method for measuring an amount of the rotation slipof the composite crystal structure;

FIG. 5 shows a characteristic of full width at half-maximum of the (333)X-ray rocking curve of the epitaxial layer as a function of changes inthe supply ration of the group VI to group II gases;

FIGS. 6(a) to 6(c) show (422) X-ray reflection intensity from the CdTeepitaxial layer with respect to the specimen's rotation angle whereinthe (422) reflection angle from the silicon substrate is defined aszero; and

FIG. 7 is a supplementary drawing to FIG. 3(b) for explaining anallowable range of the mis-orientation direction <110> of the (111)silicon substrate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The basic concept of the present invention exists in that a group II-VIcompound semiconductor epitaxial layer having a (111) plane can be grownon a (111) silicon substrate with excellent lattice-matching when a 30°in-plane rotation slip exists in the interface between the epitaxiallayer and the underlying silicon substrate. When the epitaxial layer isa CdTe layer, the lattice mismatch is reduced from 19% of the prior artto 3.4%. This is schematically shown in FIGS. 1 and 2.

FIG. 1 is a schematic top view of the lattice structure at the interfacebetween the CdTe epitaxial layer and the silicon substrate. Therespective (111) planes of the CdTe layer and the silicon substrate areparallel to the sheet of the figures. The <110> direction of the siliconsubstrate and the <110> direction of the CdTe layer lie within the <111>plane (i.e. in the sheet of the figure), and form an angle of 30°. Largehatched circles 1 represent either tellurium or cadmium atoms. In FIG.1, only a first group of atoms existing in a plane for example, Te atomsare illustrated, and a second group of atoms, (Cd atoms) are not shownin order to avoid complexity because the second group of atoms arelocated on a separated plane from that of the first group and theirpositions do not exist on mesh-like lines. Open circles 2 representupper silicon atoms and shaded circles 3 represent lower silicon atoms.

In the prior art growth wherein the <110> direction of the CdTe isparallel to the <110> direction of the silicon, the respective atomspacings of CdTe and silicon, which are designated as d_(CdTe) andd_(Si) respectively in FIG. 1, have a ratio of 1.19. This means a 19%lattice mismatch exists. However, when the CdTe layer is grown with the30° in-plane rotation slip as shown in FIG. 1, the atom spacing d_(CdTe)is to be compared with atom spacing d'_(Si), resulting in obtaining aratio of 1.034 and thereby reducing the lattice mismatch to 3.4%.

FIG. 2 illustrates an actually formed product in accordance with thepresent invention, in which a (111) silicon substrate 4 and a (111) CdTeepitaxial layer 5 formed thereon comprises the composite crystalproduct, the orientation of the (111) CdTe plane having a 30° in-planerotation slip with respect to the orientation of the underlying (111)silicon substrate.

The above rotation slip may be explained in the following way. "<110>"direction of the (111) silicon substrate 4 is taken as a referencedirection as shown by an arrow A in FIG. 2. In this case, the direction<110> of the silicon substrate lies in the (111) silicon plane. The<110> direction of the grown (111) CdTe epitaxial layer 5 as shown byeither of the arrows B or B', forms an angle of plus or minus 30° withrespect to an arrow A' the arrow A' parallel to the reference directionshown by arrow A. Since the reference direction A' is coincident witheither the <211> direction or the <121> direction of the grown (111)CdTe epitaxial layer 5, the above condition can be described such thateither <211> direction or <121> direction of the grown CdTe is parallelto the <110> direction of the silicon substrate.

In short, in order to reduce the lattice mismatch and to obtain bettercrystallinity, the (111) CdTe epitaxial layer 5 as grown on the (111)silicon substrate, is required to have 30° rotation in crystalorientation in either a forward or a backward direction with respect tothe silicon substrate.

Experiments showed that a mol ratio of DETe (group VI source gas) toDMCd (group II source gas) during the MOCVD process plays an importantrole in growing a (111) CdTe epitaxial layer with a 30° in-planerotation slip on a (111) silicon substrate, and further amis-orientation of (111) silicon substrate toward <110> direction ispreferable, to suppress twinning of the CdTe epitaxial layer. Details ofexperiments are described in the following.

[MOCVD growth conditions]

A silicon substrate is first cleaned and annealed in a hydrogenatmosphere (760 Torr) at 1000° C. Next, the temperature is decreased to400° C., and DMCd and DETe gases are introduced while maintaining thesubstrate temperature at 400° C., the partial pressure of DMCd beingcontrolled in a range from 1×10⁻² to 1×10⁻³ Torr and the partialpressure of DETe being controlled in a range from 1 to 1×10⁻² Torr.Effects of changes in the mol ratio of DETe/DMCd were tested, for valuesof the mol ratio of 1.5, 5, 15, 20, 30, and 60.

[Mis-orientation of (111) silicon]

Herein, mis-orientation of a (111) silicon substrate is defined as thesubstrate surface, the <111> direction of which is inclined by a smallangle toward a predetermined direction. This is illustrated in FIGS.3(a) and 3(b). FIG. 3(a) shows a cross section of a normal (111)substrate in which the direction <111> is vertical to the substratesurface. FIG. 3(b) shows a cross section of a mis-oriented substrate inwhich the crystal direction <111> of the substrate forms an angle θrelatively to the normal to a (i.e., vertical line); the substratesurface. If it is assumed that the substrate is inclined toward the<110> direction (in the figure, the <110> direction of the substratelies within the plane of the sheet), the mis-orientation orientation iscalled the (111) substrate mis-oriented by θ° toward the <110>direction, or the (111) substrate misoriented by θ°-off toward (i.e., θ°from the) <110> direction.

Several types of (111) silicon substrates were prepared and tested,which included different mis-orientation (inclination) angles anddifferent mis-orientation directions.

[Test methods]

The crystalline structure of the grown epitaxial layer was evaluated bya known method of measuring a full width at half-maximum (FWHM) of the(333) plane X-ray rocking curve.

In order to find whether the grown epitaxial layer has the 30° in-planerotation slip and whether it exhibits twinning or not the crystaldirection of the grown epitaxial layer was tested by measuring the X-raydiffraction intensity. This test method is briefly described using FIG.4. There exists a (422) plane, in each of the CdTe epitaxial layer andthe silicon substrate, which forms an angle of 19.5° with respect to therespective (111) planes of the epitaxial layer and substrate. When theincident X-ray has an incident angle of 35.61°, reflected X-ray has amaximum intensity. The arrangements of X-ray projection and detectionare fixed on this condition. The silicon substrate with the CdTe layeris set to be rotatable around an axis of the (111) plane. When themaximum intensity from the (422) plane of the silicon substrate isfound, this substrate position is taken as a reference such as anglezero. Next, the substrate is rotated by a specified angle from thereference position, and the reflected X-ray intensity from the (422)plane of the CdTe epitaxial layer is measured. This step is repeated bychanging the rotation angle gradually, and an X-ray intensity curveversus rotation angle is plotted.

[Test results]

Crystallinity test results of the grown CdTe epitaxial layer whichchanges in the mol ratio of DETe/DMCd, are shown, in typical fashion inFIG. 5. The FWHM value decreases (i.e. the crystallinity improves) withan increase of the DETe/DMCd ratio. A mol ratio greater than 15 ispreferable.

Typical test results for the reflection from the (422) plane are shownin FIGS. 6(a) to 6(c).

Data of FIG. 6(a) are obtained under the condition that the CdTeepitaxial growth is performed while keeping the mol ratio of DETe/DMCdat a constant value of 30, and the (111) silicon is mis-oriented towardthe <211> direction. The curve has two peaks at ±30° values of therotation angle. This means that there is a rotation slip of 30° betweenthe CdTe epitaxial layer and the silicon substrate; however, theepitaxial layer exhibits twinning.

Data of FIG. 6(b) are obtained under the condition that the CdTeepitaxial growth is performed while keeping the mol ratio of DETe/DMCdat a constant value of 15, and the (111) silicon is mis-oriented toward<211> direction, as in the case of FIG. 6(a). The curve has two peaks at±60° values of the rotation angle. Because of the symmetrical structureof a zinc-blende type crystal, this means that the grown CdTe epitaxiallayer has the same crystal orientation as that of the CdTe layer grownby the prior art method, and it has the same lattice-mismatch with thesilicon substrate.

Data of FIG. 6(c) are obtained under the condition that the CdTeepitaxial growth is performed while keeping the mol ratio of DETe/DMCdat a constant value of 30, and the (111) silicon is mis-oriented by 8°toward <110> direction. The curve has only one peak at a +30° values ofthe rotation angle. This means that there is a rotation slip of 30°between the CdTe epitaxial layer and the silicon substrate, and theepitaxial layer does not exhibit twinning. Satisfactory results areobtained in this case.

Further test where performed with changes in the mol ratio, themis-orientation direction of (111) silicon plane and the mis-orientationangle θ. Summarizing all test results, in order to obtain a 30° in-planerotation slip for (111) CdTe epitaxial on (111) silicon substrate, it isrequired that the mol ratio of DETe/DMCd be greater than 15 and that the(111) silicon substrate be mis-oriented toward the <110> direction by anangle of from 1 to 10 degrees.

The above direction <110> of mis-orientation may have an allowable anglerange of ±15° on the (111) plane. This range is schematically shown inFIG. 7. The <111> direction of the silicon substrate may be inclinedtoward either of arrows A and B, wherein the angle formed between thedirection <110> and either the arrow A or the arrow B being limited towithin 15°.

[Additional improvements]

In the above embodiments, a (111) CdTe epitaxial layer is grown on a(111) silicon substrate. When zinc is mixed in the CdTe epitaxial layer,namely, Cd_(1-x) Zn_(x) Te is grown on the (111) silicon substrate,lattice mismatch is further reduced and, in an ideal case where x=0.55,the lattice mismatch is reduced to 0%. This can be performed by addingdiethylzinc (DEZn) source gas during the MOCVD growth previouslydescribed. A partial pressure of diethylzinc gas is determined at aselected value within a range of from 10⁻² to 10⁻⁴ Torr so as to obtainthe mixing ratio x of 0.55.

Further, GaAs which has a crystal structure of a zinc-blende type can beused as a substrate in a similar way instead of using a siliconsubstrate. Further, a composite structure composed of silicon and GaAs,with the GaAs epitaxially grown on the silicon substrate, may be used asa secondary substrate.

The presently disclosed embodiments are, to be considered in allrespects as illustrative and not restrictive, the scope of the inventionbeing indicated by the appended claims, rather than the foregoingdescription, and all modifications which come within the meaning andrange of equivalence of the claims are, therefore, to be embracedtherein.

What is claimed is:
 1. A method of growing a group II-VI epitaxial layeron a substrate by a MOCVD method, the substrate being of a materialselected from the group consisting of silicon, gallium arsenide andgallium arsenide on silicon and having a (111) plane, said methodcomprising the steps of:providing a plurality of metal organic gassources respectively supplying the elements of said group II-VIepitaxial layer and flowing a carrier gas and said plurality of sourcegases over, and heating, said substrate in accordance with the MOCVDmethod, wherein the relative amounts of source gases supplied on thesubstrate has a mol ratio as defined by (group VI gas supplyvolume)/(group II gas supply volume) which is greater than 15, therebygrowing epitaxial layer on said substrate with a 30° inplane rotationalslip between the respective crystal orientations.
 2. A method of growinga group II-VI epitaxial layer on a substrate as recited in claim 1,wherein said (111) plane of the substrate is mis-oriented toward a <110>direction of said substrate.
 3. A method of growing a group II-VIepitaxial layer on a substrate as recited in claim 2, wherein saidmisorientation angle is within a range of from 1 degree to 10 degrees.4. A method of growing a group II-VI epitaxial layer on a substrate asrecited in claim 2, wherein said (111) plane is misoriented toward the<110> direction within an allowable range of plus and minus 15 degrees.5. A method of growing a group II-VI epitaxial layer on a substrate asrecited in claim 1, wherein said plurality of metal organic gas sourcescomprises a cadmium source gas and a tellurium source gas and theepitaxial layer thereby comprises a cadmium telluride (CdTe) layer.
 6. Amethod of growing a group II-VI epitaxial layer on a substrate asrecited in claim 1, wherein said plurality of metal organic gas sourcescomprises a cadmium source gas, a zinc source gas, and a telluriumsource gas and the epitaxial layer thereby comprises a cadmium zinctelluride (CdZnTe) layer being grown on the substrate.
 7. A method ofgrowing a group II-VI epitaxial layer on a substrate as recited in claim6, wherein said cadmium zinc telluride epitaxial layer has a compositionof Cd₀.45 Zn₀.55 Te.